As herbicides, proposition has been made of heterocyclic compounds substituted with phenyl groups having certain types of substituents, such as N-(substituted phenyl)-3, 4, 5, 6-tetrahydrophthalimides, 3-(substituted phenyl)-1, 5-tetramethylenehydantoins, 4-(substituted phenyl)-1, 2-tetramethyleneurazoles, 9-(substituted phenylimino)-8-thia-1, 6-diazabicyclo[4.3. 0]nonan-7-ones, 3-(substituted phenyl)-1, 3, 4-oxadiazolin-2-ones and the like. However, these compounds generally have low selectivity between weeds and crops, so they cannot satisfy both of herbicidal activity and safety for crops. Thus, they are presently put to practical use only in a limited field.
Although a great number of substituted-phenyl heterocyclic compounds with herbicidal activity have been proposed as has been described above, few of them have both the safety for significant crops and sufficient herbicidal activity, so that herbicides provided with the two properties have been expected. In case of taking account of environmental influence as well, a herbicide with less dose for application is preferable.
The present inventors have made intensive investigations on the problems described above, and have found that certain specific compounds having a tetrahydrofuran ring have characteristic properties such that the compounds have high herbicidal activity and nevertheless do not show almost any influence on a great number of significant crops. Thus, they have achieved the present invention.
That is, the gist of the present invention resides in novel tetrahydrofuran derivatives, represented by the following general formula [I]: ##STR2## {wherein A represents direct bonding or a group represented by --B--CHR.sup.1 -- (wherein B represents oxygen atom, sulfur atom or imino group; R.sup.1 represents hydrogen atom or an alkyl group of C.sub.1 -C.sub.4);
R represents hydrogen atom, halogen atom, hydroxyl group, an alkoxy group of C.sub.1 -C.sub.4, benzyloxy group, an alkylsulfonyloxy group of C.sub.1 -C.sub.3 or a group represented by --O--COR.sup.2 (wherein R.sup.2 represents an alkyl group of C.sub.1 -C.sub.5, a haloalkyl group of C.sub.1 -C.sub.3, an alkenyl group of C.sub.2 -C.sub.5, a cycloalkyl group of C.sub.3 -C.sub.6, phenyl group, benzyl group, an alkoxy group of C.sub.1 -C.sub.4, an alkylamino group of C.sub.1 -C.sub.4 or a dialkylamino group of C.sub.2 -C.sub.6);
X represents halogen atom;
Y represents hydrogen atom or halogen atom;
Z is a group represented by ##STR3## (wherein U.sup.1, U.sup.2 and U.sup.3 independently represent oxygen atom or sulfur atom; R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 independently represent an alkyl group of C.sub.1 -C.sub.4)}; and a herbicide containing the same as the active ingredient.
The compounds of the present invention will now be explained in details.
In accordance with the present invention, the tetrahydrofuran derivatives to be used as a herbicide is represented by the above general formula [I].
In the above general formula [I], A represents direct bonding or a group represented by --B--CHR.sup.1 -- (wherein B represents O, S or NH; R.sup.1 represents hydrogen atom or an alkyl group of C.sub.1 -C.sub.4 such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and the like).
R represents hydrogen, atom; halogen atom such as fluorine atom, chlorine atom, bromine atom and the like; hydroxyl group; an alkoxy group of C.sub.1 -C.sub.4 such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group and the like; benzyloxy group; an alkylsulfonyloxy group of C.sub.1 -C.sub.3 such as methylsulfonyloxy group, ethylsulfonyloxy group, n-propylsulfonyloxy group, isopropylsulfonyloxy group, and the like; or a group represented by --O--COR.sup.2 (wherein R.sup.2 represents an alkyl group of C.sub.1 -C.sub.5 such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group and the like; a haloalkyl group of C.sub.1 -C.sub.3 such as chloromethyl group, bromomethyl group, 2-chloroethyl group, 2-bromoethyl group, 3-chloropropyl group, 3-bromopropy group, difluoromethyl group, dichloromethyl group, trifluoromethyl group, trichloromethyl group, 2, 2, 2-trifluoroethyl group and the like; an alkenyl group of C.sub.2 -C.sub.5 such as vinyl group, allyl group, 1-propenyl group, 1-methylvinyl group, 2-butenyl group, 3-butenyl group, 1-methylallyl group, 2-methylallyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 3-methyl-2-butenyl group, 2-methyl-3-butenyl group, 4-pentenyl group, 3-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-3-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group and the like; a cycloalkyl group of C.sub.3 -C.sub.6 such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like; phenyl group; benzyl group; an alkoxy group of C.sub.1 -C.sub.4 such as those described above as the R; an alkylamino group of C.sub.1 -C.sub.4 such as methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, isobutylamino group, secbutylamino group, t-butylamino group and the like; or a dialkylamino group of C.sub.2 -C.sub.6 such as dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, methylethylamino group, methyl-n-propylamino group and the like.
X represents halogen atom such as those as described above as the R; Y represents hydrogen atom or halogen atom such as those described above as the R. Z is a group represented by ##STR4## (wherein U.sup.1, U.sup.2 and U.sup.3 independently represent oxygen atom or sulfur atom; R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 independently represent an alkyl group of C.sub.1 -C.sub.4 such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group and the like).
The compounds of the present invention are preferably ones wherein R represents hydrogen atom, hydroxyl group, benzyloxy group, an alkylsulfonyloxy group of C.sub.1 -C.sub.3 or a group represented by --O--COR.sup.2 (wherein R.sup.2 represents an alkyl group of C.sub.1 -C.sub.5, a haloalkyl group of C.sub.1 -C.sub.3, an alkenyl group of C.sub.2 -C.sub.5, a cycloalkyl group of C.sub.3 -C.sub.6, phenyl group, and an alkoxy group of C.sub.1 -C.sub.4 [in particular, R more preferably represents hydrogen atom, hydroxyl group or an alkylsulfonyloxy group of C.sub.1 -C.sub.3, or a group represented by --O--COR.sup.2 group (wherein R.sup.2 represents an alkyl group of C.sub.1 -C.sub.5, an alkenyl group of C.sub.2 -C.sub.5, a cycloalkyl group of C.sub.3 -C.sub.6, a phenyl group or an alkoxy group of C.sub.1 -C.sub.3)]; and Z represents a group represented by ##STR5## (wherein U.sup.1 and U.sup.2 independently represent oxygen atom or sulfur atom; R.sup.3 represents an alkyl group of C.sub.1 -C.sub.3). (As Z, the one representing ##STR6## is preferable.)
More preferable compounds are ones wherein A represents --SCH.sub.2 --; R represents a group represented by --O--COR.sup.2 (wherein R.sup.2 represents an alkyl group of C.sub.1 -C.sub.5); X and Y represent halogen atom; and Z represents ##STR7## Particularly preferable compounds include 9-(5-(4-acetoxytetrahydrofuran-3-yloxycarbonylmethylthio)-4-chloro-2-fluor ophenylimino)-8-thia-1, 6-diazabicyclo[4.3.0]nonan7-one (Compound No. 26 in Table 1 described below) shown in Example 11 described below.
The method for producing the compounds of the present invention will now be explained below.
The compounds of the present invention represented by the above general formula [I], can be synthesized, for example, by the following reaction scheme. ##STR8## (In the above reaction scheme, V.sup.1 represents halogen atom such as chlorine atom, bromine atom and the like; A, R, X, Y, and Z independently represent the same meanings as described above.)
The above reaction is carried out without a solvent or in a solvent in the presence or absence of a base, generally in a temperature range of 0.degree. to 100 .degree. C. Appropriate solvent if used includes aromatic hydrocarbons such as benzene, toluene, xylene and the like; halogenated hydrocarbons Such as dichloromethane, chloroform, 1, 2-dichloroethane and the like; ethers such as diethyl ether, tetrahydrofuran, dioxane and the like; esters such as methyl acetate, ethyl acetate and the like; ketones such as acetone, methyl ethyl ketone and the like; polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile and the like. The bases to be used include triethylamine, pyridine, picoline, N, N-dimethylaniline, sodium hydrogencarbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, sodium hydride and the like.
The starting material compound [II] can be produced by reacting the corresponding carboxylic acid XI] with a halogenating agent such as thionyl chloride, phosphorous trichloride, phosphorous tribromide and the like. The compound [XI] is described in each gazette of Japanese Patent Laid-open Nos. 149267/1982, 189178/1983, 225070/1983, 109578/1985, 149571/1985, and 76487/1986, European Patent Publication Nos. 49508, 77938 and 126419. ##STR9## (In the above scheme, A, X, Y, Z, and V.sup.1 independently represent the same meanings as described above.) ##STR10## (In the above reaction scheme, V.sup.2 represents halogen atom such as chlorine atom, bromine atom and the like; A, R.sup.2, X, Y, and Z independently represent the same meanings as described above.)
The above reaction is carried out without a solvent or in a solvent in the presence of a base, generally in a temperature range of 0.degree. to 100 .degree. C. Appropriate solvent if used includes those described in (1). The bases to be used include those described in (1).
The starting material [IV] is a compound wherein R is hydroxyl group in the compound [I] of the present invention, and can be produced by the methods shown in the process (1) described above, and the processes (3), (4), (5), (6) and (7) described below. ##STR11## (In the above reaction scheme, A, X, Y, Z and V.sup.2 independently represent the same meanings as described above; and R.sup.9 represents an alkyl group of C.sub.1 -C.sub.3 such as methyl group, ethyl group, n-propyl group, isopropyl group.)
The above reaction is carried out without a solvent or in a solvent in the presence of a base, generally in a temperature range of 0.degree. to 100 .degree. C. Appropriate solvent if used includes those described in (1). The bases to be used include those described in (1). ##STR12## (In the above reaction scheme, V.sup.3 represents halogen atom such as chlorine atom, bromine atom, iodine atom; B, R, R.sup.1, X, Y and Z independently represent the same meanings as described above.)
The above reaction is carried out without a solvent or in a solvent in the presence of a base, generally in a temperature range of room temperature to 200.degree. C. Appropriate solvent if used includes those described in (1), and besides, the bases to be used include those described in (1).
In case V.sup.3 means Cl or Br, iodide such as sodium iodide, potassium iodide, and the like may be added to acclerate the reaction.
The starting material IV] is described in each gazette of Japanese Patent Laid-open Nos. 53662/1981, 83672/1983, 189178/1983, 172491/1984, 109578/1985, 149571/1985, 233075/1985, 40261/1986, and 76487/1986, European Patent Publication No. 77938 and United Kingdom Patent Publication No. 2127410. ##STR13## (In the above reaction scheme, A, R, X, and Y independently represent the same meanings as described above.)
The above reaction is carried out without a solvent or in a solvent under heating, generally in a temperature range of 50.degree. to 200 .degree. C. Appropriate solvent if used includes water; and polar solvents including carboxylic acids such as acetic acid, alcohols such as methanol, ethanol, propanol, butanol, etc.; and the like, in addition to these described in (1).
The starting material [VII] can be produced, for example, by the method shown in the following scheme. ##STR14## (In the above scheme, A, B, R, R.sup.1, X and Y independently represent the same meanings as described above.) ##STR15## (In the reaction scheme, A, R, X, Y, and R.sup.3 independently represent the same meaning as described above.)
The above reaction is carried out without a solvent or in a solvent, generally in a temperature range of 0.degree. to 100 .degree. C. Appropriate solvent if used includes those described in (1).
The starting material [VIII] can be produced by reacting the compound [VII] described hereinabove with thiophosgene or N, N-dialkylthiocarbamoyl chloride. ##STR16## (In the scheme, A, R, X and Y independently represent the same meanings as described above; R.sup.11 represents a lower alkyl group such as methyl group, ethyl group, propyl group, butyl group and the like). ##STR17## (In the above reaction scheme, R.sup.10 represents hydrogen atom or an alkyl group of C.sub.1 -C.sub.4 such as methyl group, ethyl group, propyl group, butyl group and the like; D represents --N-- or --CH--; A, R, X, Y and U.sup.1 independently represent the same meanings as described above.)
The above reaction is carried out without a solvent or in a solvent in the presence or absence of a base, generally in a temperature range of room temperature to 200 .degree. C. Appropriate solvent if used includes polar solvents such as alcohols such as methanol, ethanol, propanol and the like; water and the like, in addition to those described in (1). The bases to be used include those described in (1).
The starting material [IX] can be produced from the compound [VII] described above, for example, by the method shown in the following scheme. In the scheme, phosgene or trichloromethyl chloroformate is used for the preparation of isocyanate (U.sup.1 =O) in the reaction of the first stage. And, thiophosgene or N, N-dialkylthiocarbamoyl chloride is used for the preparation of isothiocyanate (U.sup.1 =S). ##STR18## (In the scheme, A, R, X, Y, U.sup.1, D and R.sup.10 independently represent the same meanings as described above.) ##STR19## (In the above reaction scheme, A, R, X, Y and U.sup.2 independently represent the same meanings as described above.)
The above reaction is carried out by reacting phosgene (U.sup.2 =O) or thiophosgene (U.sup.2 =S) without a solvent or in a solvent in the presence of a base, generally in a temperature range of -10.degree. to 100 .degree. C. In case of U.sup.2 =O, trichloromethyl chloroformate can be used instead of phosgene. Appropriate solvent if used includes those descried in (1). The bases to be used include those described in (1).
The starting material [X] can be produced by reacting the compound [VIII] described above with hexahydropyridazine. ##STR20## (In the above scheme, A, R, X and Y independently represent the same meanings as described above.)
The compounds of the present invention thus obtained have isomers such as optical isomers, diastereomer and the like. The present invention includes all of them. The compounds of the present invention can be used as a herbicides singly as in the form of each of the isomers thereof or as an appropriate mixture of the isomers.
In using the compounds of the present invention as a herbicide, the technical product may be applied as it is. However, the compound is generally used in the form of wettable powder, granule, emulsifiable concentrate, flowable and the like by using appropriate auxiliaries. Example of such auxiliaries include solid carrier such as kaolin, bentonite, talc, diamatoceous earth, white carbon, carbohydrate and the like; solvents including water, alcohols (methanol, ethanol, propanol, butanol, ethylene glycol and the like), ketones (acetone, methyl ethyl ketone, cyclohexanone and the like), ethers (diethyl ether, dioxane, cellosolves and the like), aliphatic hydrocarbons (kerosin, kerosene, and the like), aromatic hydrocarbons (benzene, toluene, xylene, solvent naphtha, methylnaphthalene and the like), halogenated hydrocarbon (dichloroethane, trichlorobenzene, carbon tetrachloride and the like), amides (dimethylformamide and the like), esters (ethyl acetate, butyl acetate, fatty acid glycerin esters and the like), nitriles (acetonitrile and the like); surfactant including nonionic surfactant (polyoxyethylene alkylallyl ether, polyoxyethylene sorbitan monolaurate and the like), cationic surfactant (alkyl dimethylbenzylammonium chloride, alkylpyridium chloride and the like), anionic surfactant (alkylbenzene sulfonate, lignin sulfonate, higher alcohol sulfate and the like), amphoteric surfactant (alkyl dimethyl betaine, dodecylaminoethyl glycine and the like), and the like. These solid carriers, solvents, and surfactants are individually used in a mixture of one or two or more thereof, depending on needs.
The dose for application of the compounds of the present invention varies depending on the structure of the compound, the subjective weeds, the application time, the application method, the soil properties and the like, but the dose as the active ingredient thereof is generally in a range of 5-2000 g, preferably 10-1000 g per ha.
The subjective weeds of the compounds of the present invention are, for example, Chenopodium album, Chenopodium serotinum, Polygonum lapathifolium, Polygonum persicaria, Amaranthus lividus, Amaranthus viridis, Stellaria media, Lamium amplexicaule, Digitaria adscendens, Eleusine indica, Echinochloa Crus-galli, Setaria viridis, and the like in upland fields; in paddy fields, for example, Rotala indica, Lindernia pyridaria, Monochoria vaginalis, Dopatrium junceum, Elatine triandra, Alisma canadiculatum, Echinochloa oryzicola, Cyperus difformis, and the like. Furthermore, the compounds of the present invention exhibits high herbicidal activity on those weeds which have been hard to be controlled by known herbicides, including, for example, Abutilon theophrasti, Xanthium strumarium, Ipomoea indica, Datura Stramonium, Brassica juncea, Galium aparine, Viola tricolor, Matricaria matricarioides, Bidens pilosa, and the like in upland fields; in paddy fields, for example, Sagittaria pygmaea, Sagitaria trifolia, Scirpus juncoides, Cyperus serotinus, and the like. The compounds of the present invention show herbicidal activity against the weeds described above through the soil application in pre-emergent stage and the foliar application in post-emergent stage. The compound of the present invention also have less influence on crops such as corn, wheat, barley, sorgho, rice, soybean, potato and the like through soil application in pre-emergent stage and foliar application in post-emergent stage, and can be used as a selective herbicide.
The herbicide containing the compound of the present invention as the active ingredient can be mixed and applied with other pesticides such as, for example, insecticides, fungicides, plant growth regulators, or fertilizers. By mixing and applying with other herbicides, the herbicidal activity of the compound can be stabilized. The herbicides which can preferably be mixed with, include the following, for example:
Pyrazole herbicides; 4-(2, 4-dichlorobenzoyl)-1, 3-dimethylpyrazol-5-yl p-toluenesulfonate, 4-(2, 4-dichlorobenzoyl)-1, 3-dimethyl-5-phenacyloxypyrazole, 4-(2, 4-dichloro-3-methylbenzoyl)-1,3-dimethyl-5-(4-methylphenacyloxy)pyrazole, 4-(2, 4-dichlorobenzoyl)-1-methyl-5-phenacyloxypyrazole, and the like;
Sulfonylurea herbicides; methyl 2-(4, 6-dimethoxypyridin-2-ylcarbamoylaminosulfonylmethyl)benzoate, ethyl 5-(4, 6-dimethoxypyridin-2-ylcarbamoylaminosulfonyl)-1-methylpyrazole-4-carboxyl ate, 2-chloro-N-(4-methoxy-6-methyl-1, 3, 5-triazin-2-ylaminocarbonyl)benzene sulfonamide, methyl 2-(4-methoxy-6-methyl-1, 3, 5-triazin-2-ylcarbamoylaminosulfonyl)benzoate, methyl 2-(4, 6-dimethylpyridin-2-ylcarbamoylaminosulfonyl)benzoate, ethyl 2-(4-chloro-6-methoxypyridin-2-ylcarbamoylaminosulfonyl)benzoate, and the like;
Phenoxy herbicides; (2, 4-dichlorophenoxy)acetate and the derivatives thereof, (4-chloro-2-methylphenoxy)acetate and the derivatives thereof, 4-(4-chloro-2-methylphenoxy)butylate and the derivatives thereof, S-ethyl 4-chloro-2-methylphenoxy)thioacetate, 2-(2-naphthoxy)propione anilide, 2-(2, 4-dichloro-3-methylphenoxy)propione anilide, butyl 2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]propionate;
Haloacetanilide herbicides; 2-chloro-2', 6'-diethyl-N-methoxymethylacetanilide, 2-chloro-2',6'-diethyl-N-butoxymethylacetanilide, 2-chloro-2'-ethyl-6'-methyt-N-(2-methoxy-1-methylethyl)acetanilide, 2-chloro2',6'-diethyl-N-propoxyethylacetanilide, ethyl N-chloroacetyl-N-(2, 6-diethylphenyl)aminoacetate, 2-chloro-2',6'-dimethyl-N-(3-methoxy-2-tenylmethyl)acetanilide and the like;
Amide herbicides; 3',4'-dichloropropionanilide, 2',3'-dichloro-4-ethoxymethoxybenzanilide, 2-bromo-3,3-dimethyl-N-(.alpha.,.alpha.-dimethylbenzyl)butylic acid amide, 2-benzothiazol-2-yloxy-N-methylacetanilide, 2',4'-difluoro-2-(3-trifluoromethylphenoxy)nicotinanilide, 2,6-dimethoxy-N(3-(1-ethyl-1-methylpropyl)isoxazol-5-yl)benzamide, and the like;
Carbamate herbicides; S-(4-chlorobenzyl) N,N-diethylthiocarbamate, S-ethyl N,N-hexamethylenethiocarbamate, S-isopropyl N,N-hexamethylenethiocarbamate, S-benzyl N-ethyl-N-(1,2-dimethylpropyl)thiocarbamate, S-(1-methyl-1-phenetyl) piperidine 1-carbothioate, O-(3-t-butylphenyl) N-(6-methoxypyridin-2-yl)-N-methylthiocarbamate, S-ethyl N,N-di(n-propylthiol carbamate), S-ethyl N,N-diisobutylthiocarbamate, isopropyl N-(3-chlorophenyl)carbamate, 3-(methoxycarbonylamino)phenyl N-(3-methylphenyl)carbamate, S-(2,3-dichloroallyl) N,N-diisopropylthiocarbamate, S-(2, 3, 3-trichloroallyl) N,N-diisopropylthiocarbamate, methyl N-(4-aminobenzenesulfonyl)carbamate and the like;
Urea herbicides; 1-(.alpha.,.alpha.-dimethylbenzyl)-3-(4-methylphenyl)urea, 3-(benzothiazol-2-yl)-1,3-dimethylurea, 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-[4-(4-methylphenetyloxy)phenyl]-1-methoxy-1-methylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 1-(2-substituted benzyl)-3-(.alpha.,.alpha.-dimethylbenzyl)ureas and the like;
Diphenyl ether herbicides; 2, 4, 6-trichloro-4'-nitrodiphenyl ether, 2,4-dichloro-3'-methoxy-4'-nitrodiphenyl ether, methyl 5-(2, 4-dichlorophenoxy)-2-nitrobenzoate, 3-[5-(2-chloro-4-trifluoromethylphenoxy)2-nitrophenoxy]tetrahydrofuran, 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate and the salts thereof, 2-chloro-3'-ethoxy-4'-nitro-4-trifluoromethyldiphenyl ether, 1-(ethoxycarbonyl)ethyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate, 5-(2-chloro-4-trifluoromethylphenoxy)-N-(methylsulfonyl)-2-nitrobenzamide, methyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime-O-acetate, 3-amino-2-chloro-4-nitrodiphenyl ether and the like;
Triazine herbicides; 2-chloro-4-ethylamino-6-isopropylamino-1, 3, 5-triazine, 2, 4-bis(ethylamino)-6-methylthio-1,3,5-triazine, 2-ethylamino-4-(1,2-dimethylpropylamino)-6-methylthio-1,3,5-triazine, 2,4-bis(isopropylamino)-6-methylthio-1,3,5-triazine, 4-amino-6-t-butyl-3-methylthio-1,2,4-triazine-5(4H)-one, 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazine-5(4H)-one, 2-chloro-4,6-bis(ethylamino)-1,3,5-triazine, 2-(2-chloro-4-ethylamino-1,3,5-triazin-6-ylamino)-2-methylpropionitrile and the like;
Dinitroaniline herbicides; 2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl)aniline, N-(1-ethylpropyl)3,4-dimethyl-2,6-dinitroaniline, 3,5-dinitro-N.sup.4, N.sup.4 -dipropylsulfanilide and the like;
Nitrile herbicides; 4-hydroxy-3,5-diiodobenzonitrile, 3,5-dibromo-4-hydroxybenzonitrile, 2,6-dichlorobenzonitrile and the like;
Phosphorous-containing herbicides; O-ethyl O-(5-methyl-2-nitrophenyl) N-sec-butylphosphoroamidate, S-(2-(benzenesulfonylamino)ethyl) O,O-diisopropyl phosphorodithioate, S-((2-methylpiperidin-1-yl)carbonylmethyl) O,O-dipropyl phosphorodithioate, N-(phosphonomethyl)glycine, ammonium (DL-homoalanin-4-yl(methyl)phosphonate, sodium 4-(hydroxy(methyl)phosphinoyy)-L-homoalanyl-L-alanyl-L-alanate, and the like;
Quarternary-ammonium salts herbicides; 1,1'-ethylene-2,2'-bipyridium dibromide, 1,1'-dimethyl-4,4'-bipyridium dichloride and the like;
Other herbicides; 3,6-dichloro-2-methoxybenzoate, 3,7-dichloroquinoline-8-carboxylic acid, pentachlorophenol, 2-sec-butyl-4,6-dinitrophenol, 2-amino-3-chloro-1,4-naphthoquinone, 1,2-dihydropyridazine-3,6-dione, 3-(2methylphenoxy)pyridazine, 3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide, 2,2-dichloropropionic acid, 2,2,3,3-tetrafluoropropionic acid, methyl 6-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-3(4)-methylbenzoate, 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid and the salts thereof, 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)quinoline-3-carboxylic acid, 5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid, 1-methyl-4-(1-methylethyl)-2-((2-methylphenyl)methoxy)-7-oxabicyclo[2.2.1] heptane, 1-(3-methylphenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide, 2-(N-ethoxybutylimidyl)-5-(2-ethylthiopropyl)-3-hydroxy-2-cyclohexen-1-one , 2-(3,5-dichlorophenyl)-2-(2,2,2-trichloroethyl)oxirane, N-[4-chlorobenzyloxy)phenyl]-3,4,5,6-tetrahydrophthalimide, N-(4-chloro-2-fluoro-5-propargyloxyphenyl)-3,4,5,6-tetrahydrophthalimide, 3-(2,4-dichloro-5-isopropoxyphenyl)-5-t-butyl-1,3,4-oxadiazole-2(3H)-one, 4-methoxy-3,3'-dimethylbenzophenone, 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl methanesulfonate, 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)pyridine-4(1H)-one, 2-(2-chlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone, (E), (E)-2-(1-(3-chloropropen-2-yloxyimino)butyl)-5-(2-ethylthiopropyl)-3-hydro xy-2-cyclohexen-1-one, 2-(1-ethoxyiminopropyl)-3-hydroxy-5-dimethyl-2-dichlorohexen-1-one and the like.
These can be mixed in plurality for use.
The present invention will now be explained in details with reference with examples, but the invention is not limited to the following examples, unless departing from the scope thereof.